CN112679695B - Preparation method of high-stability organic silicon modified waterborne polyurethane - Google Patents
Preparation method of high-stability organic silicon modified waterborne polyurethane Download PDFInfo
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/61—Polysiloxanes
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Abstract
The invention relates to a preparation method of high-stability organosilicon modified waterborne polyurethane, belonging to the technical field of polyurethane materials. According to the technical scheme, silica sol is dispersed and diluted, and is mixed and modified with a silane coupling agent KH-560, then hydroxyl-terminated silicone oil is modified through succinic anhydride, so that hydroxyl-terminated silicone oil is modified into carboxyl-terminated groups, nano silicon dioxide is introduced into organic silicone oil due to the reaction of compounding and reacting of the carboxyl-terminated groups and epoxy-modified nano silicone sol, macromolecular chains are regularly enriched and arranged on the surface of an adhesive film, and water molecules are difficult to enter the adhesive film, so that the water resistance of the adhesive film is effectively improved, and meanwhile, in the modification process, the silica sol particles are tightly combined together due to the bridging effect of the hydroxyl-terminated groups of the hydroxyl-terminated silicone oil, so that approximately two silica sol particles generate a coalescence phenomenon, and the mechanical property of the prepared waterborne polyurethane material is further modified.
Description
Technical Field
The invention relates to a preparation method of high-stability organic silicon modified waterborne polyurethane, belonging to the technical field of polyurethane materials.
Background
Polyurethanes are block copolymers obtained by the stepwise polymerization of isocyanates with polyols or polyamines, mainly divided into soft and hard segments. The soft segment is composed of polyol or polyamine, is in a random curl shape, and is relatively soft; isocyanate, small molecular polyol or polyamine chain extender form a hard segment, and a carbamate group generated by the reaction and a benzene ring in the aromatic isocyanate are stretched into a rod shape at normal temperature, so that the segment is not easy to twist, and the rigidity is high. The soft segments in the molecular chain gather together and their glass transition temperature is lower than room temperature, called the rubber phase. The rigid chain segments in the molecular chain are associated with each other due to the large cohesive energy to form a plurality of small units called micro-regions, the glass transition temperature of the small units is far higher than the room temperature, and the small units are in glass states and microcrystals at the normal temperature. Due to the incompatibility of the soft and hard segments, the soft and hard segments are aggregated in the polymer to form a soft segment and a hard segment, which are separated to some extent, and the poorer the compatibility of the two segments, the higher the microphase separation. The polyurethane has the characteristics of good elasticity, wear resistance, excellent mechanical property, good low-temperature flexibility and the like due to the existence of a microphase separation structure.
The organic silicon modified waterborne polyurethane not only keeps the characteristics of wear resistance, excellent elasticity and high bonding strength with a base material of the polyurethane material, but also integrates the advantages of good low-temperature flexibility, good water resistance and excellent chemical resistance of organic silicon resin, and is a modified material with excellent performance. Because the solubility parameters of the organosilicon chain segment and the polyurethane chain segment are greatly different, the compatibility of the organosilicon chain segment and the polyurethane chain segment is poor. The organosilicon modified waterborne polyurethane is subjected to soft segment formation by organosilicon, and the polyurethane is subjected to hard segment formation by polyurethane, so that micro-phase separation to a certain extent can be formed, and the performances of emulsion and adhesive film thereof are influenced, so that the selection of a proper modification scheme is indispensable for improving the existing organosilicon modified polyurethane resin preparation scheme.
Disclosure of Invention
The invention aims to provide a preparation method of high-stability organosilicon modified waterborne polyurethane, which is used for solving one of the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the high-stability organosilicon modified waterborne polyurethane specifically comprises the following preparation steps:
(1) dispersing nano silica sol by isopropanol, and then carrying out composite modification with a silane coupling agent to prepare dispersed silica sol;
(2) taking succinic anhydride and an epoxy end-capping reagent, and modifying by using octamethylcyclotetrasiloxane and 0.1-0.2 part of tetramethylammonium hydroxide as raw materials to prepare a modified mixed solution; because the surface of the nano silicon dioxide is provided with a plurality of active silicon hydroxyls which can participate in the reaction, the silicon hydroxyls on the surface of the silane coupling agent with the epoxy group, such as gamma-glycidyl ether propyl trimethyl oxygen silane, are utilized to carry out the coupling reaction, and then the intermediate with the epoxy group is obtained.
(3) Taking polyester dihydric alcohol, toluene diisocyanate and the modified mixed solution, and adding 1, 4-butanediol and trimethylolpropane to prepare a polyurethane prepolymer in an auxiliary manner; the hydroxyl-terminated silicone oil is modified by succinic anhydride to modify the hydroxyl-terminated silicone oil into carboxyl-terminated silicone oil, the nano silicon dioxide is introduced into the organic silicone oil to modify the waterborne polyurethane due to the reaction of compounding and generating the carboxyl-terminated silicone oil and epoxy-modified nano silica sol, the content of the modified silicone oil in the waterborne polyurethane is continuously improved, the modified silicone oil has low surface tension through a Si-O-Si inorganic framework and an organic side chain structure, and simultaneously has large Si-O bond energy and polarity, a shielding effect on macromolecular chain hydrocarbon groups, large Si-O-Si bond angles, free rotation and flexibility, macromolecular chains are regularly enriched and arranged on the surface of an adhesive film, water molecules are difficult to enter the adhesive film, and therefore the water resistance of the adhesive film is effectively improved.
(4) And (3) removing the solvent after the polyurethane prepolymer is terminated to prepare the high-stability organic silicon modified waterborne polyurethane.
The nano silica sol in the step (1) has a solid content of 40%.
The silane coupling agent in the step (1) is preferably a silane coupling agent KH-560.
And (3) adding succinic anhydride into the epoxy end capping agent according to the mixing ratio of 1:5 of succinic anhydride to the epoxy end capping agent in the step (2).
The modified mixed solution in the step (2) is prepared by the following specific steps: adding succinic anhydride into an epoxy end-capping reagent according to the mass ratio of 1:5, stirring and mixing, placing at 75-85 ℃ for heat preservation reaction for 3-5 h, collecting reaction liquid, respectively weighing 45-50 parts by weight of octamethylcyclotetrasiloxane, 0.1-0.2 part by weight of tetramethylammonium hydroxide and 10-15 parts by weight of the reaction liquid, placing in an oil bath device, controlling the temperature of the oil bath to be 120-130 ℃, performing heat preservation reaction for 2-3 h, standing and cooling to room temperature to obtain modified base liquid; stirring and mixing the dispersed sol solution and the modified matrix solution according to the mass ratio of 1:15, reacting for 3-5 hours at the temperature of 75-80 ℃, performing ultrasonic dispersion for 10-15 min, filtering, and collecting filtrate to obtain modified mixed solution. Due to the bridging effect of hydroxyl at the hydroxyl end of the hydroxyl silicone oil, the silica sol particles are tightly combined together, so that about two silica sol particles are subjected to coalescence, and the mechanical property of the prepared waterborne polyurethane material is further modified.
The preparation method of the polyurethane prepolymer in the step (3) comprises the following steps: respectively weighing 45-50 parts by weight of polyester diol, 10-15 parts by weight of toluene diisocyanate and 3-5 parts by weight of modified mixed solution, placing the mixture into a three-neck flask provided with a reflux condensing device and a stirring device, stirring and mixing the mixture, placing the mixture at 75-85 ℃ for heat preservation reaction for 3-5 hours, standing and cooling the mixture to 55-65 ℃ to collect intermediate reaction liquid, adding 1, 4-butanediol into the intermediate reaction liquid according to the mass ratio of 1:15, then performing heat preservation reaction at 75-80 ℃ for 3-5 hours, collecting mixed reaction liquid, then adding trimethylolpropane into the mixed reaction liquid according to the mass ratio of 1:20, stirring and mixing the mixture, and continuing placing the mixture at 75-80 ℃ for heat preservation reaction for 45-60 minutes to obtain prepolymer.
And (4) removing the solvent by vacuum distillation at 45-50 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the technical scheme of the invention is that silica sol is dispersed and diluted and is mixed and modified with silane coupling agent KH-560, because the surface of nano-silica has a plurality of active silicon hydroxyl groups which can participate in the reaction, the silicon hydroxyl groups on the surface of the silane coupling agent with epoxy groups, such as gamma-glycidyl ether propyl trimethyl oxygen silicane, are subjected to coupling reaction to obtain an intermediate with epoxy groups, then the hydroxyl groups of the intermediate are modified by hydroxyl-terminated silicone oil through succinic anhydride to obtain terminal carboxyl groups, because the terminal carboxyl groups are compounded and reacted with epoxy-modified nano-silica sol, the nano-silica is introduced into organic silicone oil to modify the waterborne polyurethane, the content of the modified silicone oil is continuously increased in the waterborne polyurethane, the modified silicone oil has low surface tension through the Si-O-Si inorganic framework and organic side chain structure contained in the nano-silica oil, and simultaneously because the bond energy of Si-O is large, the polarity is large, the shielding effect is realized on macromolecular chain hydrocarbon groups, the Si-O-Si bond angle is large, the rotation is free, the flexibility is realized, the macromolecular chains are regularly enriched and arranged on the surface of an adhesive film, and water molecules are difficult to enter the adhesive film, so the water resistance of the adhesive film is effectively improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Adding nano silica sol with the solid content of 40% into isopropanol according to the mass ratio of 1:10, stirring, mixing and collecting diluent, dropwise adding KH-560 into the diluent according to the mass ratio of 1:15, controlling the dropwise adding speed to be 2-3 mL/min, stirring, mixing, placing under 200-300W for ultrasonic dispersion for 10-15 min after dropwise adding is completed, and collecting the dispersed sol solution; adding succinic anhydride into an epoxy end-capping reagent according to the mass ratio of 1:5, stirring and mixing, placing the mixture at 75-85 ℃ for heat preservation reaction for 3-5 h, collecting reaction liquid, respectively weighing 45-50 parts by weight of octamethylcyclotetrasiloxane, 0.1-0.2 part by weight of tetramethylammonium hydroxide and 10-15 parts by weight of the reaction liquid, placing the mixture in an oil bath device, controlling the temperature of the oil bath to be 120-130 ℃, performing heat preservation reaction for 2-3 h, standing and cooling to room temperature to obtain modified base liquid; stirring and mixing the dispersed sol solution and the modified matrix solution according to the mass ratio of 1:15, reacting for 3-5 hours at the temperature of 75-80 ℃, performing ultrasonic dispersion for 10-15 min, filtering, and collecting filtrate to obtain modified mixed solution; respectively weighing 45-50 parts by weight of polyester diol, 10-15 parts by weight of toluene diisocyanate and 3-5 parts by weight of modified mixed solution, placing the mixture into a three-neck flask provided with a reflux condensing device and a stirring device, stirring and mixing the mixture, placing the mixture at 75-85 ℃ for heat preservation reaction for 3-5 hours, standing and cooling the mixture to 55-65 ℃ to collect intermediate reaction liquid, adding 1, 4-butanediol into the intermediate reaction liquid according to the mass ratio of 1:15, then performing heat preservation reaction at 75-80 ℃ for 3-5 hours, collecting mixed reaction liquid, then adding trimethylolpropane into the mixed reaction liquid according to the mass ratio of 1:20, stirring and mixing the mixture, and continuing placing the mixture at 75-80 ℃ for heat preservation reaction for 45-60 minutes to obtain prepolymer; collecting the prepolymer, placing the prepolymer at room temperature, stirring and cooling to room temperature, adding an ethylenediamine aqueous solution with the mass fraction of 5% into the prepolymer according to the mass ratio of 1:8, carrying out end-capping reaction, then carrying out reduced pressure distillation, and removing the solvent to obtain the high-stability organic silicon modified waterborne polyurethane.
Example 1
Adding nano silica sol with the solid content of 40% into isopropanol according to the mass ratio of 1:10, stirring and mixing, collecting diluent, dropwise adding KH-560 into the diluent according to the mass ratio of 1:15, controlling the dropwise adding rate to be 2mL/min, stirring and mixing after dropwise adding, placing under 200W for ultrasonic dispersion for 10min, and collecting dispersed sol solution; adding succinic anhydride into an epoxy end-capping reagent according to the mass ratio of 1:5, stirring and mixing, placing at 75 ℃ for heat preservation reaction for 3 hours, collecting reaction liquid, respectively weighing 450 parts of octamethylcyclotetrasiloxane, 0.1 part of tetramethylammonium hydroxide and 10 parts of reaction liquid by weight, placing in an oil bath device, controlling the oil bath temperature to be 120 ℃, performing heat preservation reaction for 2 hours, and standing and cooling to room temperature to obtain modified base liquid; stirring and mixing the dispersed sol solution and the modified matrix solution according to the mass ratio of 1:15, reacting for 3 hours at the temperature of 75 ℃, performing ultrasonic dispersion for 10 minutes, filtering, and collecting filtrate to obtain modified mixed solution; respectively weighing 45 parts by weight of polyester diol, 10 parts by weight of toluene diisocyanate and 3 parts by weight of modified mixed solution, placing the mixture into a three-neck flask provided with a reflux condensing device and a stirring device, stirring and mixing the mixture, placing the mixture into a heat preservation reaction at 75 ℃ for 3 hours, standing and cooling the mixture to 55 ℃ to collect intermediate reaction liquid, adding 1, 4-butanediol into the intermediate reaction liquid according to the mass ratio of 1:15, performing heat preservation reaction at 75 ℃ for 3 hours, collecting mixed reaction liquid, then adding trimethylolpropane into the mixed reaction liquid according to the mass ratio of 1:20, stirring and mixing the mixture, and continuing the heat preservation reaction at 75 ℃ for 45 minutes to obtain a prepolymer; collecting the prepolymer, placing the prepolymer at room temperature, stirring and cooling to room temperature, adding an ethylenediamine aqueous solution with the mass fraction of 5% into the prepolymer according to the mass ratio of 1:8, carrying out end-capping reaction, then carrying out reduced pressure distillation, and removing the solvent to obtain the high-stability organic silicon modified waterborne polyurethane.
Example 2
Adding nano silica sol with the solid content of 40% into isopropanol according to the mass ratio of 1:10, stirring and mixing, collecting diluent, dropwise adding KH-560 into the diluent according to the mass ratio of 1:15, controlling the dropwise adding rate to be 2mL/min, stirring and mixing after dropwise adding, placing under 250W for ultrasonic dispersion for 12min, and collecting dispersed sol solution; adding succinic anhydride into an epoxy end-capping reagent according to the mass ratio of 1:5, stirring and mixing, placing at 77 ℃ for heat preservation reaction for 4 hours, collecting reaction liquid, respectively weighing 47 parts of octamethylcyclotetrasiloxane, 0.1 part of tetramethylammonium hydroxide and 12 parts of reaction liquid by weight, placing in an oil bath device, controlling the oil bath temperature to 125 ℃, performing heat preservation reaction for 2 hours, and standing and cooling to room temperature to obtain modified base liquid; stirring and mixing the dispersed sol solution and the modified matrix solution according to the mass ratio of 1:15, reacting at the temperature of 77 ℃ for 4 hours under heat preservation, performing ultrasonic dispersion for 12 minutes, filtering, and collecting filtrate to obtain modified mixed solution; respectively weighing 47 parts by weight of polyester diol, 12 parts by weight of toluene diisocyanate and 4 parts by weight of modified mixed solution, placing the polyester diol, 12 parts by weight of toluene diisocyanate and 4 parts by weight of modified mixed solution into a three-neck flask provided with a reflux condensing device and a stirring device, stirring, mixing, placing the mixture at 80 ℃ for heat preservation reaction for 4 hours, standing, cooling to 60 ℃ to collect intermediate reaction liquid, adding 1, 4-butanediol into the intermediate reaction liquid according to the mass ratio of 1:15, performing heat preservation reaction for 4 hours at 77 ℃, collecting mixed reaction liquid, then adding trimethylolpropane into the mixed reaction liquid according to the mass ratio of 1:20, stirring, mixing, and continuing to perform heat preservation reaction for 52 minutes at 77 ℃ to obtain prepolymer; collecting the prepolymer, placing the prepolymer at room temperature, stirring and cooling to room temperature, adding an ethylenediamine aqueous solution with the mass fraction of 5% into the prepolymer according to the mass ratio of 1:8, carrying out end-capping reaction, then carrying out reduced pressure distillation, and removing the solvent to obtain the high-stability organic silicon modified waterborne polyurethane.
Example 3
Adding nano silica sol with the solid content of 40% into isopropanol according to the mass ratio of 1:10, stirring, mixing and collecting diluent, dropwise adding KH-560 into the diluent according to the mass ratio of 1:15, controlling the dropwise adding speed to be 3mL/min, stirring, mixing, placing under 300W for ultrasonic dispersion for 15min after dropwise adding is completed, and collecting the dispersed sol solution; adding succinic anhydride into an epoxy end-capping reagent according to the mass ratio of 1:5, stirring and mixing, placing the mixture at 85 ℃ for heat preservation reaction for 5 hours, collecting reaction liquid, respectively weighing 50 parts by weight of octamethylcyclotetrasiloxane, 0.2 part by weight of tetramethylammonium hydroxide and 15 parts by weight of the reaction liquid, placing the mixture in an oil bath device, controlling the temperature of the oil bath to be 130 ℃, performing heat preservation reaction for 3 hours, and standing and cooling to room temperature to obtain modified base liquid; stirring and mixing the dispersed sol solution and the modified matrix solution according to the mass ratio of 1:15, reacting for 5 hours at the temperature of 80 ℃, performing ultrasonic dispersion for 15min, filtering, and collecting filtrate to obtain modified mixed solution; respectively weighing 50 parts by weight of polyester diol, 15 parts by weight of toluene diisocyanate and 5 parts by weight of modified mixed solution, placing the mixture into a three-neck flask provided with a reflux condensing device and a stirring device, stirring, mixing, placing the mixture into a heat preservation reaction at 85 ℃ for 5 hours, standing, cooling to 65 ℃, collecting an intermediate reaction solution, adding 1, 4-butanediol into the intermediate reaction solution according to the mass ratio of 1:15, performing heat preservation reaction at 80 ℃ for 5 hours, collecting a mixed reaction solution, adding trimethylolpropane into the mixed reaction solution according to the mass ratio of 1:20, stirring, mixing, and continuously placing the mixed reaction solution at 80 ℃ for heat preservation reaction for 60 minutes to obtain a prepolymer; collecting the prepolymer, placing the prepolymer at room temperature, stirring and cooling to room temperature, adding an ethylenediamine aqueous solution with the mass fraction of 5% into the prepolymer according to the mass ratio of 1:8, carrying out end-capping reaction, then carrying out reduced pressure distillation, and removing the solvent to obtain the high-stability organic silicon modified waterborne polyurethane.
Example 4
Respectively weighing 50 parts by weight of polyester diol, 15 parts by weight of toluene diisocyanate and 5 parts by weight of hydroxyl-terminated silicone oil, placing the polyester diol, 15 parts by weight of toluene diisocyanate and 5 parts by weight of hydroxyl-terminated silicone oil into a three-neck flask provided with a reflux condensing device and a stirring device, stirring, mixing, placing the mixture at 85 ℃ for heat preservation reaction for 5 hours, standing and cooling the mixture to 65 ℃ to obtain an intermediate reaction liquid, adding 1, 4-butanediol into the intermediate reaction liquid according to a mass ratio of 1:15, performing heat preservation reaction at 80 ℃ for 5 hours, collecting a mixed reaction liquid, then adding trimethylolpropane into the mixed reaction liquid according to a mass ratio of 1:20, stirring, mixing, and continuously placing the mixed reaction liquid at 80 ℃ for heat preservation reaction for 60 minutes to obtain a prepolymer; collecting the prepolymer, placing the prepolymer at room temperature, stirring and cooling to room temperature, adding an ethylenediamine aqueous solution with the mass fraction of 5% into the prepolymer according to the mass ratio of 1:8, carrying out end-capping reaction, then carrying out reduced pressure distillation, and removing the solvent to obtain the high-stability organic silicon modified waterborne polyurethane.
The performance of the waterborne polyurethane prepared by the invention is tested in the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4,
1. water absorption:
weighing a film with the mass of W1, soaking the film in deionized water for 24 times, taking out the film, wiping off liquid on the surface of the film by using filter paper, then weighing the film with the mass of W2, and calculating the water absorption rate according to the following formula:
water absorption (%) = [ (W2-W1)/Wl ] × 100%.
2. Mechanical properties
The mechanical property of the adhesive film is that the adhesive film sample is made into a 10mm x 70mm strip by a mould, then the thickness of each sample is measured by taking 3 points to be measured at the central position of each sample by a screw micrometer, and then the average value is taken. After the sample is balanced for 24 hours under the conditions of constant temperature and constant humidity, the load value and the absolute length at the time of fracture are recorded by measuring the sample on an SH2-3 electronic universal material testing machine, the clamping length of the sample is 30mm, and the stretching speed is 250 mm/min. The tensile strength and elongation at break of the film were calculated according to the following formulas:
tensile strength (Mpa) = breaking load value (N)/thickness of film (mm) × width of film (mm).
Elongation at break (%) = absolute length (mm)/grip length (mm)
TABLE 1 comparison of Properties
From the above table, it can be seen that examples 1, 2 and 3 prepared by the present invention have excellent mechanical properties and water resistance, and the water resistance can reflect the stability of the internal structure of the polyurethane material, and meanwhile, in comparison with example 4, the mechanical properties and water resistance are significantly reduced compared with examples 1, 2 and 3, which indicates that the technical scheme of the present invention is that the hydroxyl-terminated silicone oil is modified by succinic anhydride to modify the hydroxyl-terminated silicone oil into carboxyl-terminated groups, and the nano-silica is introduced into the organic silicone oil due to the reaction of the combination and the reaction of the carboxyl-terminated groups and the epoxy-modified nano-silica sol to modify the waterborne polyurethane, so that the content of the modified silicone oil in the waterborne polyurethane is continuously increased, and the modified silicone oil has low surface tension through the Si-O-Si inorganic skeleton and the organic side chain structure contained in the waterborne polyurethane, meanwhile, because the Si-O bond energy is large, the polarity is large, the macromolecular chain hydrocarbon group is shielded, the Si-O-Si bond angle is large, the rotation is free, the flexibility is realized, the macromolecular chains are regularly enriched and arranged on the surface of the adhesive film, and water molecules are difficult to enter the adhesive film, the water resistance of the adhesive film is effectively improved, and meanwhile, in the modification process, due to the bridging effect of hydroxyl groups at the hydroxyl ends of hydroxyl silicone oil, the silica sol particles are tightly combined together, so that about two silica sol particles are subjected to coalescence, and the mechanical property of the prepared waterborne polyurethane material is further modified.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (1)
1. A preparation method of high-stability organosilicon modified waterborne polyurethane is characterized by comprising the following specific preparation steps:
(1) adding nano silica sol with the solid content of 40% into isopropanol according to the mass ratio of 1:10, stirring, mixing and collecting diluent, dropwise adding KH-560 into the diluent according to the mass ratio of 1:15, controlling the dropwise adding speed to be 2mL/min, stirring, mixing, placing under 250W for ultrasonic dispersion for 12min after dropwise adding is completed, and collecting the dispersed sol solution;
(2) adding succinic anhydride into an epoxy end-capping reagent according to the mass ratio of 1:5, stirring and mixing, placing at 77 ℃ for heat preservation reaction for 4 hours, collecting reaction liquid, respectively weighing 47 parts of octamethylcyclotetrasiloxane, 0.1 part of tetramethylammonium hydroxide and 12 parts of reaction liquid by weight, placing in an oil bath device, controlling the oil bath temperature to 125 ℃, performing heat preservation reaction for 2 hours, and standing and cooling to room temperature to obtain modified base liquid; stirring and mixing the dispersed sol solution and the modified matrix solution according to the mass ratio of 1:15, reacting at the temperature of 77 ℃ for 4 hours under heat preservation, ultrasonically dispersing for 12 minutes, filtering, and collecting filtrate to obtain modified mixed solution;
(3) respectively weighing 47 parts by weight of polyester diol, 12 parts by weight of toluene diisocyanate and 4 parts by weight of modified mixed solution, placing the polyester diol, 12 parts by weight of toluene diisocyanate and 4 parts by weight of modified mixed solution into a three-neck flask provided with a reflux condensing device and a stirring device, stirring, mixing, placing the mixture at 80 ℃ for heat preservation reaction for 4 hours, standing, cooling to 60 ℃ to collect intermediate reaction liquid, adding 1, 4-butanediol into the intermediate reaction liquid according to the mass ratio of 1:15, performing heat preservation reaction for 4 hours at 77 ℃, collecting mixed reaction liquid, then adding trimethylolpropane into the mixed reaction liquid according to the mass ratio of 1:20, stirring, mixing, and continuing to perform heat preservation reaction for 52 minutes at 77 ℃ to obtain prepolymer;
(4) collecting the prepolymer, placing the prepolymer at room temperature, stirring and cooling to room temperature, adding an ethylenediamine aqueous solution with the mass fraction of 5% into the prepolymer according to the mass ratio of 1:8, carrying out end-capping reaction, then carrying out reduced pressure distillation, and removing the solvent to obtain the high-stability organic silicon modified waterborne polyurethane.
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